Herbicidal agents

ABSTRACT

3-(HYDROGEN-, (UNSUBSTITUTED AND HALO, AMINO, ALKYLAMINO, NITRO, ALKYL, ALKOXY, ALKYLMERCAPTO, ARYLOXY AND/OR HALOARYLMERCAPTO, SUBSTITUTED) ALIPHATIC-, CYCLOALIPHATIC-, ARALIPHATIC-, ARYL-, OR N-heterocyclic- or O-alkanoyl-, -substituted oxy, mercapto or amino)- 4-(amino; mono and di (unsubstituted and cyano, hydroxy and/or halo, -substituted) alkyl- and/or alkanoyl-, -amino; N(unsubstituted and cycloalkyl, aryl, haloaryl, alkaryl, alkoxy aryl, nitroaryl, halo-nitro-aryl, aryl-alkenyl, heterocyclic and/or nitro- heterocyclic- -substituted) alkylidene-amino or cycloalkylidene- amino; or N-heterocyclic)-6-((unsubstituted and halo, nitro, carbo lower alkoxy, alkyl, alkoxy, aryloxy, alkylmercapto, arylmercapto and/or aralkylmercapto, -substituted) aliphatic, cycloaliphatic, araliphatic, aryl, heterocyclic or heterocyclic- alkyl)-1,2,4-triazine-5-ones, which possess herbicidal properties, and which may be produced by conventional methods; herbicidal compositions containing such compounds; and methods of using such compounds as herbicides.

United States Patent Westphal et al.

[ 1 June 20, 1972 [54] HERBICIDAL AGENTS [72] Inventors: Kurt Westphal,Wuppertal-Vohwinkel; Werner Meiser, Wuppertal-Elberfeld; Ludwig Fue,Cologne-Stammheim; Helmuth Hack, Cologne-Buchheim, all of GermanyFarbeniabriken Bayer Aktiengesellschaft, Leverkusen, Germany [22] Filed:Jan. 28, 1970 [21] Appl.No.: 6,647

[73] Assignee:

Related U.S. Application Data [63] Continuation-in-part 0f Ser. No.630,225, April 12,

[30] Foreign Application Priority Data April 16, 1966 Germany ..F 48954[56] References Cited UNITED STATES PATENTS 3,544,570 12/1970 Timmler eta1. ..260/249.5

OTHER PUBLICATIONS Dornow et al., Chem. Ber., vol. 97, pp. 2173- 8(1964) Primary E.\'aminer.lohn M. Ford AnorneyBurgess, Dinklage & Sprung5 71 ABSTRACT 3-[hydrogen-, (unsubstituted and halo, amino, alkylamino,nitro, alkyl, alkoxy, alkylmercapto, aryloxy and/or haloarylmercapto,-substituted) aliphatic-, cycloaliphatic-, araliphaticaryl-, orN-heterocyclicor O-alkanoyl-, -substituted oxy, mercapto or amin0]-4-[amino; mono and di (unsubstituted and cyano, hydroxy and/or halo,-substituted) alkyland/or alkanoy1-, -amino; N (unsubstituted andcycloalkyl, aryl, haloaryl, alkaryl, alkoxy aryl, nitroaryl,halo-nitro-aryl, arylalkenyl, heterocyclic and/or nitroheterocyclic--substituted) alkylidene-amino or cycloalkylideneamino; orN-heterocyclic]-6-[(unsubstituted and halo, nitro, carbo lower alkoxy,alkyl, alkoxy, aryloxy, alkylmercapto, arylmercapto and/oraralkylmercapto, -substituted) aliphatic, cycloaliphatic, araliphatic,aryl, heterocyclic or heterocyclicalkyl]-1,2,4- triazine-S-ones, whichpossess herbicidal properties, and which may be produced by conventionalmethods; herbicidal compositions containing such compounds; and methodsof using such compounds as herbicides.

16 Claims, No Drawings HERBICIDAL AGENTS This is a continuation-in-partapplication of copending U.S. application Ser. No. 630,225, filed Apr.12, 1967.

The present invention relates to and has for its objects the provisionfor particular substituted 4-amino-1,2,4-triazine- 5- ones, some ofwhich are known, which possess valuable, especially selective,herbicidal properties, active compositions in the form of mixturesthereof with solid and liquid dispersible carrier vehicles, and methodsfor their preparation and use, especially for combating weeds, undesiredplants, and the like; with other and further objects of this inventionbecoming apparent from a study of the within specification andaccompanying examples.

It is known that 1,3,5 -triazines can be used for the control of weeds(see Belgian Pat. No. 540,590). In this group of active compounds,2,6-di-(ethylamino)-4-chloro-l,3,5-triazine (A) has attained aconsiderable practical significance.

It has now been found, in accordance with the present invention, thatthe particular 4-arnino-1,2,4-triazine-5-ones having the formula inwhich R is selected from the group consisting of aliphatic having 1-18carbon atoms, cycloaliphatic having 5-10 ring carbon atoms, araliphatichaving 6-10 ring carbon atoms in the corresponding aryl moiety and 1-4carbon atoms in the aliphatic moiety, aryl having 6-10 ring carbonatoms, heterocyclic having 5-6 ring members with at least one heterolinking atom selected from the group consisting of O, N, S and mixturesof such hetero atoms, heterocyclic-lower alkyl in which the heterocyclicmoiety has 5-6 ring members with at least one hetero linking atomselected from the group consisting of O, N, S and mixtures of suchhetero atoms, and such aliphatic, cycloaliphatic, araliphatic, aryl,heterocyclic and heterocyclic-lower alkyl, respectively, which issubstituted with at least one substituent selected from the groupconsisting of halo, nitro, carbo lower alkoxy, lower alkyl, loweralkoxy, aryloxy having 6-10 ring carbon atoms, lower alkylmercapto,arylmercapto having 6-10 ring carbon atoms, aryl-lower alkylmercaptohaving 6-10 ring carbon atoms in the aryl moiety, and mixtures of suchsubstituents;

R, and R, each respectively is selected from the group consisting ofhydrogen, alkyl having 1-12 carbon atoms, alkanoyl having 1-6 carbonatoms, and such alkyl and alkanoyl, respectively, which is substitutedwith at least one substituent selected from the group consisting ofcyano, hydroxy, halo, and mixtures of such substituents,

with the proviso that R, and R, when taken together represent alkylidenehaving 1-12 carbon atoms, cycloalkylidene having 5-8 ring carbon atoms,and such alkylidene and cycloalkylidene, respectively, which issubstituted with at least one substituent selected from the groupconsisting of cycloalkyl having 5-8 ring carbon atoms, aryl having 6-10ring carbon atoms, haloaryl having 6-10 ring carbon atoms, lower alkylaryl having 6-10 ring carbon atoms in the aryl moiety, lower alkoxy arylhaving 6-10 ring carbon atoms in the aryl moiety,

nitroaryl having 6-10 ring carbon atoms, halo-nitroaryl with the furtherproviso that R, and R, when taken together with the adjacent N atomrepresent N-containing heterocyclic having 5-6 ring members;

Y is selected from the group consisting of O, S and and R, and R, eachrespectively is selected from the group consisting of hydrogen,aliphatic having 1-18 carbon atoms, cycloaliphatic having 5-8 ringcarbon atoms, araliphatic having 6-10 ring carbon atoms in thecorresponding aryl moiety and 1-4 carbon atoms in the aliphatic moiety,aryl having 6-10 ring carbon atoms, and such aliphatic, cycloaliphatic,araliphatic and aryl, respectively, which is substituted with at leastone substituent selected from the group consisting of halo, amino, loweralkyl substituted amino, nitro, lower alkyl, lower alkoxy, loweralkylmercapto, aryloxy having 6-10 ring carbon atoms, haloarylmercaptohaving 6-10 ring carbon atoms, and mixtures of such substituents,

with the proviso that R, and R, when taken together with the adjacent Natom represent N-containing heterocyclic having 5-6 ring members; and

with the further proviso that when Y is 0 then R may also be loweralkanoyl;

exhibit strong herbicidal properties.

It is very surprising that the particular active compounds usableaccording to the present invention not only show a stronger herbicidalactivity than the known triazines in preemergence application but alsoshow a good herbicidal activity when used according to thepost-emergence method. Apart from this, the instant compounds also showmarked selective herbicidal properties (see Examples 1 and 2hereinbelow).

Some of the 1,2,4-triazine-5-ones usable according to the presentinvention are already known from the literature (cf. Chemische Berichte97, 2173-2178, 1964).

The following compounds are new: 1,2,4-triazine-5-ones of the aboveformula (1) wherein correspondingly:

a. R, R,, R, and R; are the same as defined above, and Y is oxygen,provided that R; may also be said alkanoyl;

b. R is aliphatic hydrocarbon having at least two, or at least three, orat least four, or at least five, or at least six, or more (i.e., 2-18 or3-18 or 4-18 or 5-18 or 6-18, etc), carbon atoms, or said cycloaliphatichydrocarbon, araliphatic hydrocarbon, heterocyclic or heterocyclicalkylwhich, in each case, may be substituted with one or more of said halo,nitro, carboalkoxy, alkyl, alkoxy, aryloxy, alkylmercapto, arylmercaptoand/or aryl-alkylmercapto, or R is said aryl which is substituted withone or more of said halo, nitro, carboalkoxy, alkyl, alltoxy, aryloxy,alkylmercapto, arylmercapto and/or aryl-alkylmercapto,

R,, R, and R, are the same as defined above, and

Y is sulfur; or

c. R, R, and R, are the same as defined above,

R; is aliphatic hydrocarbon having at least two, or at least three, orat least four, or at least five, or at least six, or more (i.e., 2-18 or3-18 or 4-18 or 5-18 or 6-18, etc.), carbon atoms, or saidcycloaliphatic hydrocarbon, araliphatic hydrocarbon or aryl which, ineach case, may be substituted with one or more of said halo, amino,alkyl substituted amino, nitro, alkyl, alkoxy, alkylmercapto, aryloxyand/or haloarylmercapto, and

Y is sulfur; or

d. R and R; are the same as defined above,

R, and R, each individually is said alkyl or acyl, i.e., al-

kanoyl, which may be substituted with one or more of said cyano, hydroxyand/or halo, or R, and R, taken jointly represent said alkylidene orcycloalkylidene, which, in each case, may be substituted with one ormore of said cycloalkyl, aryl, haloaryl, alkylaryl, alkoxy aryl,nitroaryl, halo-nitro-aryl, aryl-alkenyl, heterocyclic and/ornitro-hetero-cyclic or preferably represent alkylidene having at leasttwo, or at least three, or at least four, or at least five, or at leastsix, or more (i.e., 2-18 or 3-18 or 4-18 or 5-18 or 6-18, etc.), carbonatoms which is substituted with said aryl, or preferably represent saidunsubstituted cycloalkylidene, or R, and R,, together with the adjacentnitrogen atom, represent said heterocylic, and

Y is sulfur; or

e. R is aliphatic hydrocarbon having at least two, or at least three, orat least four, or at least five, or at least six, or more, (i.e., 2-18,3-18, 4-18, 5-18, 6-18, etc.), carbon atoms, or said cycloaliphatichydrocarbon, araliphatic hydrocarbon, heterocylic or heterocylic-alkylwhich, in each case, may be substituted with one or more of said halo,nitro, carboalkoxy, alkyl, alkoxy, aryloxy, alkylmercapto, arylmercaptoand/or aryl-alkylmercapto, or R is said aryl which is substituted withone or more of said halo, nitro, carboalkoxy, alkyl, alkoxy, aryloxy,alkylmercapto, arylmercapto and/or aryl-alkylmercapto,

R R R and R are the same as defined above, and

f. R, R and R, are the same as defined above,

R, and R each individually is said alkyl or acyl, i.e., al-

kanoyl, which may be substituted with one or more of said cyano, hydroxyand/or halo, or R and R taken jointly represent said alkylidene orcycloalkylidene, which, in each case, may be substituted with one ormore of said cycloalkyl, aryl, haloaryl, alkylaryl, alkoxy aryl,nitroaryl, halo-nitro-aryl, aryl-alkenyl, heterocyclic and/ornitro-heterocylic, or preferably represent alky- Iidene having at leasttwo, or at least three, or at least four, or at least five, or at leastsix, or more (i.e., 2-18 or 3-18 or 4-18 or 5-18 or 6-18, etc.), carbonatoms which is substituted with said aryl, or preferably represent saidunsubstituted cycloalkylidene, or R and R,, together with the adjacentnitrogen atom, represent said heterocyclic, and I g. R, R, and R, arethe same as defined above,

R is hydrogen and R is unsubstituted aliphatic hydrocarbon having up tothree carbon atoms, or said substituted aliphatic hydrocarbon,substituted or unsubstituted cycloaliphatic hydrocarbon, substitutedaraliphatic or substituted aryl, or R, and R each individually is saidsubi. stltuted or unsubstituted aliphatic hydrocarbon, cycloaliphatichydrocarbon, araliphatic hydrocarbon or aryl, or R, and R together withthe adjacent nitrogen atom, represent oxygen-free N-containingheterocyclic having 5-6 ring members which may be substituted with oneor more halo, amino, alkyl substituted amino, nitro, alkyl, alkoxy,alkylmercapto, aryloxy, and/or halo arylmercapto, and

The instant new triazionones can be prepared according to the customarymethods in the same manner as the known triazinones [see for exampleBerichte 97, 2,l73-2,l78

Advantageously, the instant triazinones influence plant growth and canbe used as defoliants, desiccants or herbicides and in particular asweed-killers.

By defoliants and desiccants are meant the customary harvest auxiliarieswhich are used for removing the leaves from and for drying out the greenportions of plants before bringing in the harvest.

By weeds are meant in the widest sense all plants which grow in placeswhere they are undesired.

The instant triazinones can be used as total herbicides for thedestruction of weeds, and also as selective herbicides for thedestruction of weeds in connection with the cultivation of specificagricultural crops. Whether the instant triazinones act as totalherbicides or as selective herbicides depends largely aware of thepresent invention will appreciate. Examples of crops for which thetriazinones of the instant invention are suitable are cereals (such asoats, barley, rice, maize and in particular wheat), cotton, carrots,snap beans, peas, potatoes, beets, and the like.

As weeds which can be destroyed in accordance with the presentinvention, there may be mentioned as illustrative examples:dicotyledons, such as mustard (Sinapis), cress (Lepidium), cleaver(Galium), common chickweed (Stellaria), camomile (Matricaria),smallflower Galinsoga (Galinsoga), fathen (Chenopodium), burning nettle(Urtica), groundsel (Senecio); monocotyledons, such as Timothy (Phleum),meadow grass (Poa), fescue grass (Fesruca), goosegrass 15 (Eleusine),foxtail (Setaria), ryegrass (Lolium), brome grass (Bromus), barnyardgrass (Echinochloa), and the like.

The active compounds according to the instant invention can be utilized,if desired, in the form of the usual forrnulations or compositions withdispersible carrier vehicles, such as solutions, emulsions, suspensions,emulsifiable concentrates, spray powders, pastes, soluble powders,dusting agents, granulates, etc. These are prepared in known manner, forinstance by extending the active agents with dispersible liquid diluentcarriers and/or dispersible solid carriers optionally with the use ofcarrier vehicle assistants, e.g., surface-active agents, in-

cluding emulsifying agents and/or dispersing agents, whereby, forexample, in the case where water is used as diluent, organic solventsmay be added as auxiliary solvents (see Agricultural Chemicals, March1960, pp. 35-38). The following may be chiefly considered for use ascarrier vehicles for this purpose: dispersible liquid diluent carn'ers,such as aromatic hydrocarbons (for instance, benzene, toluene, xylene,etc.), halogenated, especially chlorinated, aromatic hydrocarbons (forinstance, chlorobenzenes), paraffins (for instance,

petroleum fractions), chlorinated aliphatic hydrocarbons (for instance,methylene chloride, etc), alcohols (for instance, methanol, ethanol,propanol, butanol, etc.), ethers, ether-alcohols (for instance, glycolmonomethyl ether, etc.), amines (for instance, ethanolamine, etc.),amides (for instance 5 40 dimethyl formamide, etc.), sulfoxides (forinstance, dimethyl sulfoxide, etc.), ketones (for instance, acetone,etc.), and water; as well as dispersible finely divided solid carriers,such as ground natural minerals (for instance, kaolins, alumina, silica,chalk, i.e., calcium carbonate, talc, kieselguhr, etc.), and groundsynthetic minerals (for instance, highly dispersed silicic acid,silicates, e.g., alkali silicates, etc.); whereas the following may bechiefly considered for use as carrier vehicle assistants, e.g.,surface-active agents, for this purpose: emulsifying agents, such asnonionic and anionic emulsifying agents (for instance, polyethyleneoxide esters of fatty acids, polyethylene oxide ethers of fattyalcohols, alkyl sulfonates, aryl sulfonates, etc., and especially alkylarylpolyglycol ethers, magnesium stearate, sodium oleate, etc.); anddispersing agents, such as lignin, sulfite waste liquors, methylcellulose,

etc.

As will be appreciated by the artisan, the active compounds according tothe instant invention may be present in such formulations orcompositions in the form of mixtures with one 60, another and with otherknown active substances such as for example known herbicides includingureas, other triazines, uracils, aminotriazole, phenoxy carboxylicacids, benzoic acid, picolinic acid, and the like, if desired.

The substances according to the invention may be em- 6 5 ployed,therefore, by themselves as the artisan will appreciate,

in the form of their compositions with solid or liquid dispersiblecarrier vehicles or other known compatible active agents, or in the formof particular dosage preparations for specific application madetherefrom, such as solutions, emulsions,

suspensions, powders, pastes, and granulates which are thus ready foruse.

As concerns commercially marketed preparations, these generallycontemplate carrier composition mixtures in which the active compound ispresent in an amount substantially on the concentration thereof which isused as the artisan between about 0.1 and percent by weight, andpreferably 0.5 and 90 percent by weight, of the mixture, whereas carriercomposition mixtures suitable for direct application or fieldapplication generally contemplate those in which the active compound ispresent in an amount substantially between about 0.001 and 1.0 percent,preferably 0.005 and 0.5 percent, by weight of the mixture. Thus, thepresent invention contemplates over-all compositions which comprisemixtures of a dispersible carrier vehicle such as a dispersible carriersolid, or a dispersible carrier liquid preferably including a carriervehicle assistant, e.g., a surface'active agent, such as an emulsifyingagent and/or a dispersing agent, and an amount of the active compoundwhich is effective for the purpose in question and which is generallybetween about 0.001 and 95 percent by weight of the mixture.Specifically, the active compound may be applied to a surface area, suchas in preemergence use, in concentrations substantially between about0.5 and 20 kg per hectare, preferably between about l and kg perhectare, although it will be appreciated that in connection with thepre-emergence use of the instant compounds, as well as thepost-emergence use thereof, the concentration may be varied within afairly wide range. However, generally the postemergence range ofconcentration will be between about 0.001 and 95 percent, preferablybetween about 0,005 and 95 percent, by weight of the mixture asaforesaid, while the preemergence range will be between about 0.5 and20, preferably between about 1 and 10, kg per hectare, as aforesaid.

Furthermore, the present invention contemplates methods of selectivelycontrolling or combatting undesired plants, e.g., weeds and the like,which comprise applying to at least one of (a) such weeds and (b) theirhabitat, a herbicidally effective amount of the particular activecompound of the invention alone or together with a carrier vehicle asnoted above. The instant formulations or compositions are applied in theusual manner, for example, by spraying, atomizing, scattering, dust ing,watering, sprinkling, dispersing, and the like, whether for TABLE 1.PRE-

EXAMPLE 1 Pre-emergence test Solvent: Emulsifier:

5 parts by weight acetone 1 part by weight benzyloxypolyglycol ether Toproduce a suitable preparation of the particular active compound, 1 partby weight of such active compound is mixed with the stated amount ofsolvent, the stated amount of emulsifier is then added and the resultingconcentrate is thereafter diluted with water to the desired finalconcentration.

Seeds of the test plants are sown in normal soil and, after 24 hours,watered with the preparation of the given active compound. lt isexpedient to keep constant the amount of water per unit area. Theconcentration of the particular active compound in the preparation is ofno importance, only the amount of active compound applied per unit areabeing decisive. After three weeks, the degree of damage to the testplants is determined and characterized by the values 0-5, which have thefollowing meaning:

l slight damage or delay in growth 2 marked damage or inhibition ofgrowth 3 heavy damage and only deficient development or only percentemerged 4 plants partially destroyed after germination or only 25percent emerged 5 plants completely dead or not emerged.

The particular active compounds, the amounts applied and the resultsobtained can be seen from the following Table l:

EMERGENCE TEST Active compound I used in kg] Cheno- Galin Ecluno- AvenuActive compound hectare Oats Wheat Cotton Sinapis podium soga chloalutua (A) (l 5 4 4 5 5 5 5 3-1 5 2. 5 4 3 4 5 5 5 3 4 C 1.25 .l J 3 '3 55 L 3 r ll 5 ll 1 .\C C.\ 11 C; N C 11;

Known from Belgian Patent 540,590,:

(18) O 5 5 5 3 5 5 5 5 5 2. 5 5 5 l 5 5 5 5 5 1 25 '4 0 5 s 5 4-5 IS-XII.

u \l\ /,'-S(. H;

(2) o s V 5 5 s 5 s 5 5 2. 5 5 5 5 5 5 5 5 l. 25 4-5 4-5 5 5 5 5 5 n cx11,

N C C:

\'ew compound) 3 t l0 3 l U 5 5 5 5 5 l 0 U 5 5 5 4 t 2. 5 l U 0 4 5 5 Jr N NH;

\ C s cm;

lNEW compound) The following instant compound a having the appropriatesubstituents designated in Table 1A for Formula (I) act in the same wayas active compound (la):

The following instant compounds having the appropriate substituentsdesignated in Table 18 for Formula (I) above act in the same way asactive compound (2), which has a pronouncedly total-herbicidal action:

TABLE 113 R R1 R; R; in Y (14 a i H I ('ll; S Nr-wcmnpound.

i :rm f' \0/ (15). v w a .7 Cl]; i, s 1m.

( y :CH-/ y (l6) .7 f x I! ll CH Cll; Do.

(17 =C(CH1 1 tttttt .7 (111: a t V H Do.

(18) c. C: t t c V .7 5 U0 '19 :ClI-CIUCHm cm .7 Im.

(20 a a. -(.HOH CC]; ll (11: v t S [10.

21; a V a. CHm ClL ll ll (111-; a a 5 lm, .v ill ll ll C113 7 Do.lSOCsHn ll ll CH1 Do. (24) C li nll ll Cll; S U0,

The following instant compounds having the appropriate substitutentsdesignated in Table 1C for Formula (I) above act in the same way asactive compound (3), which exhibits selectively herbicidal action inwheat and cotton:

Post-emergence test Solvent:

5 parts by weight acetone Emulsifier:

l part by weight benzyloxypolyglycol ether until just dew moist. Afterthree weeks, the degree of damage to the plants is determined andcharacterized by the values 0-5, which have the following meaning:

no effect a few slightly burnt spots marked damage to leaves some leavesand parts of stalks partially dead plant partially destroyed plantcompletely dead bulQ-O The particular active compounds, theirconcentrations and the results obtained can be seen from the followingTable 2:

TABLE 2.POST-EME R GENCE TEST Concentration of active compound, Cheno-Stella- ()nlm- Echino- Active com pound percent Wheat Slnapis podium riaDaucus soga uhloa (A) C l 0. 1 4 5 5 5 3 4-5 4 0. 05 2 5 5 5 1 4 3 (I 0.025 l 5 4 5 U 2 J 0. 01 u 4 3 4 u 1 1 II 43' a /l N- C 6 1 H r C 2 C 2(Known from Belgian Patent (la) 0 0. 1 4 5 5 5 5 5 5 i U. 05 2 5 5 5 5 55 0. 025 l 5 5 5 5 5 5 I 0. 01 0 5 5 5 5 5 5 l N N 5 CH:

TABLE 2'.POST-EME RG ENCE TEST Concentration of active compound, Snap Cln-no- Stel- Ualin- Echino- Active compound percent Wheat Carrots beansSinapis podium lariu so za cliloa (21) O 0. 05 5 5 5 5 5 5 5 5 0. 025 55 5 5 5 5 5 5 C 0. 01 4-5 5 5 5 5 J 5 5 'ClImCH-C 1\'I\'lL Ix C -scm(New compound (28) O 0. 05 1 5 l .3 5 5 5 5 0. 025 U 5 0 5 5 5 5 5 C 0.01 5 U 5 5 5 4 4 (:SCH;

(New compound TABLE 2.POST-EMERGENCE TEST-( oomed Concentration A i i iof active compound, Snap Cheno- Stel- Galin- Echino- Active compoundpercent Wheat Carrots beans Sinapis podium laria soga chlou (26) 0 0.050 0 5 5 5 5 5 5 {I 0.025 0 0 5 5 5 5 5 4 c 0.01 0 0 4 5 5 4 5 3 if NC-NHCHzCH=CH2 (New compound) The following instant compounds having theappropriate subw 7 stitutents designated in Table 2A for Formula (1)above act in the same way as active compound (la):

TABLE 2A 0 l RC N-N H g N R2 N Y-Ra R R1 R2 R3 R4 Y (2921) CHF H H OH3 SH H OH s New compound.

( u H II CH s Do.

Cl -CH2 Q H II OH2CECH S D0.

( Q H H -CH2CHECH1 S D0.

(7) G H H -CzH H N Do.

( a Ii H OH; 0 D0 9' H H CHa H N H H -cH, H N Do 01 CHr- OH: H H CHs 3D0- CH-CH2- (a4) CH3 H H CH5 H N 3 Q H H CH2-CHz-OCHrCHz N The followinginstant compounds having the appropriate substituents designated inTable 2B for Formula (I) above act in the same way as active compound(21), which has a pronouncedly total-herbicidal action:

TABLE 2B R R1 R1 R3 R4 Y -CH3 S New compound. :CH 0

(16') H H -cH3 CH3 N Do.

H H H CH s nov (20') -CHOHCC13 H CII: 5 D0.

H H CH: S Do.

(23') iSO CsHu- The following instant compounds having the appropriatesubstituents designated in Table 2C for Formula (I) above act in thesame way as active compound (28), which exhibits a 74g carbohydrazideare heated to 90l00 C with 600 ml water. 74g pyroracemic acid are addeddropwise, with stirring. After 3 hours, filtering off cold with suctionis effected to pronouncedly selective-herbicidal action in snap beansand yield: wheat: V (36) 3-hydroxy-4-amino-6-methyl-l,Lftriazine-S-one,

TABLE 20 R R1 R3 R3 R4 Y ou -ou, s New compound.

k (:m (27/) :o CH= s Do.

(19') :CHCH(CH;)2 CH3 s Do.

(22') 0,1 H H -CH3 8 Do.

(24') s CsHun- H 11 CH:; s c 8 D- The following instant compounds havingthe appropriate sub- 7 mp. 159 C (from alcohol). stituents designated inTable 2D for Formula (I) above act in In analogous manner there are alsoobtained for instance: the same way as active compound (26), which has apronoun- (37) 3-hydroxy-4-amino-6 benzyl-l,2,4-triazine--one, cedlyselective-herbicidal action in wheat and carrots: g mp. l 73" C TABLE21) R 1 R1 R3 R4 Y (a!) II 11 C2H5 S New compound.

(17) =C(CH:)2 CH: S D0.

() =CHlQJ-NOz CH= S De.

EXAMPLE 3 (3 8) 3-hydroxy-4-amino-6-phenyl-1,2,4-triazine-5-one,Defoliant test m.p. 195 C There is prepared, in the same manner asdescribed in Example 1, an active compound preparation which contains0.05 percent of one.

A field of dwarf beans is sprayed with this preparation of the activecompound so that the dwarf beans themselves are only just dripping wet.

After 8 days the leaves are completely dried up.

The harvesting of the beans is quite considerably facilitated in thismanner.

The same action is exercised by:

( 29a 3-methylthio-4-amino-6-methyll ,2,4-triazine-5-3-methylthio-4-amino-6-phenyl- 1 ,2,4-tria.zine-5- one ( 73-ethylamino-4-amino-6-phenyll ,2 ,4-triazine-5 one (3 3'3-methoxy-4-amino-6-phenyll ,2,4-triazine-5-one.

EXAMPLl'A Preparation of 3-hydroxy-l,2,4-triuzitte-5-ones with differentsubstltuents in the 6-positionz EXAMPLE 5 Modification of 3-hydroxyl,2,4-triazine-5-ones:

20.4g 3-hydroxy-4-amino-6-phenyll ,2,4-triazine-5-one (38) are dissolvedin 300 ml dimethylformamide and cc 2N sodium methylate solution. Theexcess methanol is then distilled off in a vacuum, and 13.5gB-diethylaminoethyl chloride are added dropwise at C, with stirring, tothe remaining dimethylformamide solution. Afier a short time thereaction mixture is neutral to phenolphthalein. The solvent is distilledoff under reduced pressure. The residue is taken up in water andmethylene chloride, and the organic phase is separated and fractionallydistilled to yield:

(39) S-(B-diethylaminoethoxy)-4amino-6-phenyl-l ,2,4-

triazine-S-one, b.p. C/0.0l mm Hg.

EXAMPLE 5A Substitution products of 3-hydroxy-l,2,4-triazin-5-ones,indirect method of preparation:

2.3 g sodium are added to 500 ml methanol whereby a sodium methylatesolution is formed. 23.4g3-methylthio-4-aminoo-phenyl-l,2,4-triazin-5-one (la) and 6.5 ml methyliodide are added. The mixture is boiled for 1 hour. When cooling downthe mixture, a crystalline precipitate separates. The crystals areremoved by suction and recrystallized front methanol and optionally oncemore from acetic acid ester. The 3-methoxy-4-umino-o-phenyll.2,4-triuzin-5-one (33 thus obtained has a melting point of l67 C (89)3-methylthio-4-amino-6-styryl-1,2,4-triazine-5-one,

m.p. 218 C (90) 3-methylthio-4-amino-6-carbomethoxy-methyl-l ,2,4

-triazine--one, m.p. 1 12 C (91)3-methylthio-4-amino-6-(3-methyl-phenyl)-l,2,4-

triazine-S-one, m.p. 160C (92)3-methylthio4-amino-6-(4-methyl-phenyl)-1,2,4-

triazine-S-one, m.p. 185C (93)3-methylthio-4-amino-6-(3'-chloro-phenyl)-1,2,4-

triazine-S-one, m.p. 219 C (94)3-methylthio-4-amino-6-(3-methoxy-phenyl)-l,2,4-

triazine-S-one, m.p. 142 C (95)3-methylthio-4-amino-6-benzylmercapto-methyl- 1,2,4-triazine-5-one, m.p.110 C EXAMPLE 9 Modification of 3-methylthio- 1 ,2,4-triazine-5-ones:

1 1.7g 3-methylthio-4-amino-6-methyl-1,2,4-triazine-5-one (29a") and 15gp-chloraniline are stirred together with each other for 1 hour at 150 Cand then 1 hour at 160 C. After this the melt has become solid. Aftercooling, the melt is boiled out with ether. The insoluble portion isdissolved in, and allowed to crystallize (without filtration) from,dimethylformamide. There is obtained (96)3-(4'-chlorophenylamino)-4-amino-6-methyl-1,2,4-

triazine-S-one, m.p. 242 C When, instead of p-chloraniline, an amine isused with which, because of its volatility, the above-mentioned reactiontemperatures cannot be achieved in an open vessel, the work is carriedout in an autoclavev The following compounds for instance can also beprepared in this manner:

(97) 3-(3',4'-dichlorphenylamino)-4-amino-6-methyl-1,2,4-triazine-5-one, m.p. 228 C (98)3-(2,4'-dichlorphenylamino)-4-amino-6-methyl- 1,2,4-triazine-5-one, m.p.218 C (99) 3-(B-diethylaminoethylamino)-4-amino-6-methyl-1,2,4-triazine-5-one, m.p. 108 C (34)3-methylamino-4-amino-6-methyl-1,2,4-triazine-5- one, m.p. 180 C (7")3-ethylamino-4-amino-6-phenyl-1,2,4-triazine-5- one, m.p. 158 C (9")3-methylamino-4-amino-6-phenyl-l,2,4-triazine-5- one, m.p. 212 C 100a)3-n-buty1amino-4-amino-6-pheny1-1 ,2,4-triazine- S-one, m.p. 182 C 12')3-n-propylamino-4-amino-6-phenyl-1,2,4-triazine- S-one, m.p. 176 C 13a3-morpholino-4-amino-6-phenyl-1,2,4-triazine-5- one, m.p. 163 C (1013-(B-diethylaminoethylamino)-4-amino-6-phenyll,2,4-triazine-5one, m.p.130 C 102a) 3-benzylamino-4-amino-6-phenyl-1 ,2,4-triazine-5- one, m.p.177 C (103) 3-(4"-chloranilino)-4-amino-6-phenyl-1,2,4-

triazine-S-one, m.p. 257 C (104) 3-(4'-chloranilino)-4-amino-6-(4'-chlorbenzyl)- 1,2,4-triazine-5-one, m.p. 212 C (105)3-(B-diethylaminoethylamino)-4-amino-6-(4- chlorobenzyl)-l,2,4-triazine-5-one, m.p. 148 C3-methylamino-4-amino-6-(4'-chlorbenzyl)-1,2,4-

triazine-S-one, m.p. 159 C (106)3-benzylamino-4-amino-6-(4'-chlorbenzyl)-l ,2,4-

triazine-S-one, m.p. 123C (107)3-(fi-diethylaminoethylamino)-4-amino-6-(4'-chlorphenyl)-1,2,4-triazine-5-one, m.p. 184 C (25')3-piperidino-4-amino-6-phenyl-1,2,4-triazine-5- one, m.p. 149 C (26")3-ally1amino-4-amino-6-phenyl-1,2,4-triazine-5- one, m.p. 168 C 108)3-octadecylamino-4-amino-6-pheny1-1,2,4-triazine- S-one, m.p. 129 C(109) 3-n-hexylamino-4-amino-6phenyl-1,2,4-triazine-5- one,m.p. 164C (110) 3-[2'-(ethyl)-hexylamino]-4-amino-6-pheny1-l,2,4-

triazine-5-one,m.p. 131C 1 8 (16")3-dimethylamino-4-amino-6-phenyl-1,2,4-triazine- S-one, m.p. 133C.

EXAMPLE 10 Preparation of 3,4-diamino-1,2,4-triazine-5-ones:

43g 1,3-diamino-guanidine-hydrobromide are dissolved in a little water;38g benzoylformic acid, dissolved in methanol, are added. After briefheating, cooling is effected followed by neutralization withbicarbonate. There is obtained in this way (1 12a)3,4-diamino-6-phenyl-1,2,4-triazine-S-one, m.p.

1n analogous manner, with p-chlorbenzoylformic acid there is prepared (113) 3,4-diamino-6-(4'-chlorphenyl)-1,2,4-triazine-5-one,

m .p. 25 5 C.

EXAMPLE 11 Preparation of 3-methylthio-4-acetylamino-6-phenyl-l ,2,4-triazine-S-one:

20g 3-methylthio-4-amino-6-phenyl-1,2,4-triazine-5-one (1a") are boiledfor 9 hours with cc acetic anhydride. The excess anhydride is thendistilled ofi under reduced pressure. The crystalline residue isdissolved in, and allowed to crystallize (without filtration) from,alcohol to yield:

(6') 3-methylthio-4-diacetylamino-6-phenyl-1,2,4-

triazine-S-one, m.p. 122 C.

20g of this last mentioned compound are dissolved in alcohol and treatedat 20 C with an equivalent of 2N sodium hydroxide solution, which isconsumed very rapidly. After working up, there is obtained (8)3-methylthio-4-acetylamino-6-phenyl-1,2,4-triazine- S-one, m.p. 213C.

EXAMPLE 12 Modification of 3-methylthio-4-amino-l,2,4-triazine-5-one atthe amino group:

23.4g 3-methylthio-4-amino-6-phenyl-1,2,4-triazine-5-one (1a") aredissolved in 100 ml chlorobenzene with 17.8g freshly distilled chloraland 0.2g p-toluenesulfonic acid. The reaction mixture is heated for 1hour on a water-bath and then for 45 minutes under reflux. A smallamount of undissolved matter is filtered off hot. From the filtratethere crystallizes (20") 3-methylthio-4-(Btrichloro-a-hydroxyethyl)-amino-6-phenyl-1,2,4-triazine-5-one.

After dissolving in, and allowing to crystallize (without filtration)from, chloroform, such product has: m.p. 147 C (decomp) EXAMPLE 12AModification of 3-methylthio-4-amino-l ,2,4-triazine-5-ones by -ylidenesubstitution at the 4-position amino group:

1 1.7g 3-methylthio-4-amino-6-pheny1-1,2,4-triazine-5-one (1a""") and5.6g cyclohexanone are boiled for 1 hour in 50 ml methanol after theaddition of 5 drops of concentrated hydrochloric acid. The crystalswhich have precipitated during cooling are dissolved in, and allowed torecrystallize (without filtration) from, methanol to yield: 183-methylthio-4-cyclohexylidene-amino--phenyl- 1,2,4-triazine-5-one, m.p.C.

1n analogous manner, there are also obtained for instance:

( 15 3-methylthio-4-benzylidene-amino-6-pheny1-1,2,4-

triazine-S-one, m.p. C

(14")3-methylthio-4-(furfur-2-ylidene-amino)-6-phenyl-1,2,4-triazine-5-one,m.p. 172 C (35') 3-methylthio-4-(5'-nitro-furfur-2'-ylidene-amino)-6-phenyl-1,2,4-triazine-5-one, m.p. 207 C (17")3-methylthio-4-(prop-2-y1idene-amino)-6-phenyl- 1,2,4-triazine-5-one,m.p. 152 C (19") 3-methylthio-4-(isobutylidene-amino)-6-phenyl-1,2,4-triazine-5-one, m.p. 136 C (27") 3-methylthio-4-( l'-pheny1-eth-1'-ylidene-amino)- 6-phenyll ,2,4-triazine-5-one, m.p. 154C (28") 3-methylthio-4-(pyrid-2'-yl-methylidene-amino)-6-phenyl-1,2,4-triazine-5-one, m.p. 205 C EXAMPLE 13 In the same manner asdescribed in Example 4, using corresponding molar amounts of theappropriate starting materials the following compounds are produced:

(1 14) 3-naphth-l '-yl-n-propyloxy-4-isooctylamino-6-hex- 3 ,6 7 1 ,5 23 23 2,4, ric acid. Stirring is effected for several hours at 30 C,until the (231) 3-methylamino-4-( furfur-2-ylidene-amino )-6- resultingprecipitation of the corresponding hydrochloride salttert.-butyl-1,2,4triazine-5-one, m.p. 142 C ceases. The hydrochloridesalt is separated by suction filtra- (232) 3-methylamino-4-(prop-2'-ylidene-amino)-6-tert.-

and the ethanol solution butyl-l,2,4-triazine-5-one, m.p. 99C of 10 mlof concentrated (233) 3-methylamino-4-(4-chloro-benzylidene amino y thefollowing compound crystal- 6-tert.-butyl-1,2,4-triazine-5-one, m.p. 147C.

EXAMPLE 24 (230) 3-methylamino-4-(benzylidene-amino)-6-tert.- Theprocedure of Example 1 is repeated, and the particular butyl-l,2,4-triazine-5-one, m.p. 146 C active compounds tested, the amountsapplied, and the results In analogous manner, the following compoundsare also obobtained can be seen from the following Table 1D: t ed:

am TABLE 1D.PRE EMERGENCE TEST Active u s i Cheno- EchinokgJhectare OatsWheat Cotton Sinapis podium chloa tion, dissolved in 50 ml of ethanolrendered alkaline by the addition aqueous ammonia whereb lizes out:

Active compound Active compound Active compound N-NH: -III-H CHr-CH=CH2Active compound used in kgJhectare chlon sogu larla Oats Wheat Activecompound u u-U S-CHr-CECH (HULNVH (IOBLHVU

2. Substituted 1,2,4-triazine-5-one according to claim 1 wherein Y isselected from the group consisting of O, S; and a''. when Y is O, R isselected from the group consisting of C1 5 alkyl, cyclohexyl, phenyl andbenzyl, R1 is selected from the group consisting of hydrogen, C1 4alkyl, 1-hydroxy-2,2,2-trichloro-ethyl and acetyl, R2 is selected fromthe group consisting of hydrogen and aceTyl, and R3 is selected from thegroup consisting of hydrogen, C1 6 alkyl, C2 4 alkenyl, C2 4 alkynyl,dichloro-C2 4 alkenyl, di C1 4 alkylamino-C1 4 alkyl and acetyl; andb''. when Y is S, R is selected from the group consisting of C3 6 alkyl,cyclohexyl, adamantyl, C1 4 alkoxy-carbonylmethyl, chlorophenyl, C1 4alkyl-phenyl, C1 4 alkoxy-phenyl, nitrophenyl, benzyl, chlorobenzyl,styryl, benzylmercaptomethyl, furyl, furfuryl, pyranyl andpyridyl-methyl, R1 is selected from the group consisting of hydrogen, C14 alkyl, 1-hydroxy-2,2,2-trichloro-ethyl and acetyl, R2 is selected fromthe group consisting of hydrogen, C1 4 alkyl and acetyl, with theproviso that R1 and R2 when taken together represent a member selectedfrom the group consisting of C1 8 alkylidene, C5 6 cycloalkylidene,hexahydrobenzylidene, phenyl-C1 4 alkylidene, cinnamylidene, mono and dichlorobenzylidene, C1 4 alkyl-benzylidene, C1 4 alkoxy-benzylidene,nitrobenzylidene and chloro-nitro-benzylidene, and R3 is selected fromthe group consisting of hydrogen, C1 18 alkyl, C2 4 alkenyl, C2 4alkynyl, dichloro-C2 4 alkenyl, di C1 4 alkylamino-C1 4 alkyl, C1 4alkylmercapto-C1 4 alkyl, cyclohexyl, benzyl, chlorobenzyl andchlorophenylmercaptomethyl.
 3. Compound according to claim 1 wherein Yis S, R is selected from the group consisting of C2 5 alkyl andcyclohexyl, R1 and R2 each respectively is selected from the groupconsisting of hydrogen and hydroxy-trichloro-C2 4 alkyl, with theproviso that R1 and R2 when taken together represent a member selectedfrom the group consisting of C3 4 alkylidene and cyclohexylidene, and R3is C1 3 alkyl.
 4. Compound according to claim 1 wherein Y is S, R isselected from the group consisting of C3 5 branched chain alkyl andcyclohexyl, R1 is hydrogen, R2 is selected from the group consisting ofhydrogen and 1-hydroxy-2,2,2-trichloro-ethyl, with the proviso that R1and R2 when taken together represent a member selected from the groupconsisting of C3 4 branched chain alkylidene and cyclohexylidene, and R3is C1 2 alkyl.
 5. Substituted 1,2,4-triazine-5-one according to claim 1wherein such substituted compound is3-methylthio-4-amino-6-cyclohexyl-1, 2,4-triazine-5-one.
 6. Substituted1,2,4-triazine-5-one according to claim 1 wherein such substitutedcompound is 3-ethylthio-4-amino-6-phenyl-1,2,4-triazine-5-one. 7.Substituted 1,2,4-triazine-5-one according to claim 1 wherein suchsubstituted compound is3-methylthio-4-amino-6-benzyl-1,2,4-triazine-5-one.
 8. Substituted1,2,4-triazine-5-one according to claim 1 wherein such substitutedcompound is 3-methylthio-4-amino-6-isopropyl-1, 2,4-triazine-5-one. 9.Substituted 1,2,4-triazine-5-one according to claim 1 wherein suchsubstituted compound is3-methylthio-4-amino-6-ethyl-1,2,4-triazine-5-one.
 10. Substituted1,2,4-triazine-5-one according to claim 1 wherein Y is S, R is branchedlower alkyl or cycloalkyl, R3 is lower alkyl, and R1 and R2 areindividually hydrogen or taken together are cycloalkylidene having 5-8ring carbon atoms or alkylidene having 1-12 CARBON atoms substitutedwith carbocyclic aryl having 6-10 ring carbon atoms.
 11. Substituted1,2,4-triazine-5-one according to claim 10 wherein R is branched butyl,R3 is methyl and R1 and R2 are individually hydrogen or taken togetherare cyclopentylidene, cyclohexylidene or lower alkylidene substitutedwith phenyl, nitrophenyl, lower alkyl phenyl or lower alkoxy phenyl. 12.Substituted 1,2,4-triazine-5-one according to claim 11 wherein R1 and R2are each hydrogen.
 13. Substituted 1,2,4-triazine-5-one according toclaim 11 wherein R1 and R2 taken together are cyclopentylidene,cyclohexylidene or lower alkylidene substituted with phenyl,nitrophenyl, lower alkyl phenyl or lower alkoxy phenyl.
 14. Substituted1,2,4-triazine-5-one according to claim 13 wherein R is tert.-butyl. 15.Substituted 1,2,4-triazine-5-one according to claim 14 wherein R1 and R2taken together are benzylidene.
 16. Substituted 1,2,4-triazine-5-oneaccording to claim 14 wherein such substituted compound is3-methylthio-4-cyclohexylideneamino-6-tert.-butyl-1,2,4-triazine-5-one.